Chlorination of isopropyl alcohol



H. E. BUC. CHLORINATION 0F lsoPRoPYL ALcoH APPLICATION FILED NOV. 4,1920.

A .Patented Nov. 2l, 1922..

'process to the accom Ultimi" Si aras andere rarest ortica.

HYYM E. BUC, OF ROSELLE, NEW JERSEY, ASSIGNOR, BY MESNE ASSIGNTKENTS, T0

STANDD DEVELOPMENT COMANY, F NEW YORK, N. Y., A CORPORATION 0E DELAWARE,

CEILORINATION 0E' SOPBOPYL ALCHOL.

Application filed November 4, lt). `Serie1 No. 421,730..

To all whom t may concern.'

Be it known that I, I-IYYM Et BUo, a citizen of the United States, residing at Rolle, in the county of Union and State of ew ful Improvement in the Chlorination of Isopropyl Alcohol, of which the following is a specification.

The present invention relates to the chlorination of isopropyl alcohol, and more particularly to its chlorination for the production of chlor-acetones. It will be fully understood from the -following specification, illustrated by the accompanying drawing, which shows diagrammatically and partially in section apparatus suitable for carrying out the invention.

In accordance with the present invention isopropyl alcohol, either anhydrous or in the presence of water, is subjected to the actionof chlorine, preferably in excess, under controlled conditions of temperature such that chlor-acetones are formed and the formation of chlor-hydrocarbons` is inhibited'. The chlor-acetones are then separated vfrom the unreacted-upon alcohol and water,

if any be present, and are found to comprise dichloracetone (asyrn.) and trichloracetone (such as 1.3.3) with varying, but relatively small, amounts of tetrachloracetone (sym.) and pentachlora'cetone.

In order that the present invention may be clearly understood, reference is made in the following detailed description of the panying drawing, in which the numeral indicates a supply receptable for isopropyl alcohol, which discharges-the alcohol through a valve 11 and tube 12 formed to provide a U-shaped liquid trap into the top of tower 13. rI he tower4 is provided near its bottoni with a perforat= ed plate 14 which supports the packing material l5 which fills the tower. This acking material may be of a suitable inert su stance, such as pumice, coke, ceramic material or the like. A pipe 16, shown as passing through the top of the tower, extends to a point below the perforated supporting plate 14 and serves for the introduction of chlo` rine gas into the bottom of the tower. The

` tower is provided at its bottom with a discharge outlet 17, through which it empties into a suitable receptacle 18. The tower 13 is provided 'with a suitable jacket 19 Jersey, have invented a new and use- 'ranged in series.

mately 12% Vmay be necessary during having inlet and outlet openings and 2l for v the introduction media as required.

At its top an outlet pipe 22 leading into a cooled re`` flux condenser 23, fromwhich4 a gas escape conduit 24 leads to the. absorbers 25, 25, ar-

In carrying out the invention isopropyl alcohol, which may-contain some water, (for example, the constant boiling point mixture containing approxi-y water by volume) is fed slowly from'container 10 through trapped pipe 12 into the top Yof tower i mitted at the same time through .pipe 16 and rises in the tower in countercurrent to the descending liquid. The-rate of flow of the chlorine is adjusted so as to provide an excess over that required b the reaction, this being clearl-ly shown by the passage of chlorine throng the system into the absorbers. The temperature in the tower is controlled, if necessary, by the circulation of heated or cooled water through jacket 19 so as to be above C. and preferably not above 70 C. At working temperatures between C. and C. ei'licient about 65 C, T e reaction takes place at temperatures above C., but at such higher temperature excessive amounts of chlorinated hydrocarbons are formed Fwith corresponding reduction in the yields of chloracetones. oped by the reaction in the tower is sucient to maintain the desired temperature of reaction or even to necessitate cooling. ,Where dilute isopropyl alcohol, or isopropyl alcohol which has been already subjected to reaction with chlorine, is treated, heating the entire reaction.

The liquid products of reaction in the tower descend into receptacle 18, in which there is a separation into two layers; a lower, heavy layer comprising principally chloracetones, and an upper layer containing unreacted-upon isopropyl alcohol, water and HC1 formed in the reaction, together with some water-soluble chloracetones. Vapor products of reaction together with excess 'chlorine pass ofi through the re-lux con,

the tower' 13 is pleaded with' process of the present' yields are secured, the optimum tem erature of operation being of heating or cooling 13. Chlorine is ad-' I Ordinarily the heat devel- 50 an intermediate in the manufacture of pentachloracetone, as described in my coend.

which contain water. chloracetones are deposited as a lower olly layer and some are dissolved in the water present. Thev oily layer of chloracetones from the absorbers may be combined with that from the receptacle 18, and the aqueous liquid separately treated for recovery of the chloracetones therefrom. The oily liquid will, in general, contain chlorinated hydrocarbons, the proportion of which will` not exceed 10 to 20% when the temperature of the reaction is maintained at from 45 to 65 C.. When direct chlorination of-isopropyl alcohol, to a' further extent, say to pentachloracetone, is attempted, excessive uantities 'of chlorinated hydrocarbons are ormed, which are chlorinated to a high degree giving them a high boiling range, and rendering separation from pentachloracetone very diiiicult.

The chloracetones dissolved in the upper layer of liquid in receiver 18, and those dissolved in the aqueous liquid in the absorbers may be separated'by fractional distillation or preferably by adding to the chloracetone-containing,liquid a suitable water soluble inorganic compound, such as NaCl, CaCl2, or HC1, this process being designated salting out The separated chloracetones may be added to the combined heavier layer of liquid from the 'receiver and absorbers. The mixed chlorl acetones consist largely of dichloracetone (asym.) and trichloracetone, (such as 1.3.3) with relatively small, but varying quantities of tetrachlcracetone and pentachloracetone, together with from 10 to 20% of chlorinated hydrocarbons. The mixture has a specific gravity varying from 1.45 to 1.50, and amounts to from 200 to 225% by weight of the isopropyl alcohol reacted upon. practical separation of the chlorinated hydrocarbons may be eEected by ractionally distilling ofi" that portion of the mixture boiling below 118 C., the boiling point of unsymmetri'cal dichloracetone, the major portion of the Chlor-hydrocarbons being thereby separated. j

The upper layer of liquid in receiver' 18 maybe returned to the top of the tower in order to be again treated with chlorine,vand this may be repeated again and again until the concentration of isopropyl alcohol is so far decreased that the reaction becomes ineffective. As the 'concentration of isopropyl alcohol decreases, heating becomes necessary to maintain the proper temperature of reaction in the tower. l

The mixture of chloracetones may be utilized as suchfor example, as solvents, or as ing application Ser. No: 421729, filed o even date herewith, or the mixture may be treat ed for the separation ofthe individual chlor- In the latter some acetones, as described in my co-pending application Ser. No. 421,728, also filed of even date herewith.

It is apparent that the reaction between the chlorine and the isopropyl alcohol may be carried out by passing the chlorine into a body ofisopropyl alcohol `or in successiorl through -a series of bodies of isopropyl alcohol, while maintaining the necessary temperature of reaction. If desired the reaction may be carried out with a superatmospheric pressure of chlorine.

Although the present invention has been described in connection with the details of a specific method for carrying it into eect and of apparatus for use in connection therewith, it is `not intended that these details shall be regarded as limitations upon the scope of the invention, except in so far as included in the accompanying claims.

I claim:

1. In 'the process of forming chlorinated acetones, subjecting isopropyl alcohol to the action of chlorine-while maintaining a temperature above 35 C. and not above 70 C.

2. In the process of forming chlorinated acetones, subjecting isopropyl alcohol to the action of chlorine in excess'while maintaining a temperature .of approximately C.

3. In the process of forming chlorinated acetones, subjecting isopropyl alcohol to the action of chlorine in excess while maintaining a temperature of approximately 65 C., permitting the liquid products of reaction to separate by dii'erjence in density, and again subjecting the lighter li uid containing'unreacted-upon isopropyl a cohol to the action of chlorine under like conditions.

4. In the process of forming chlorinated acetones, subjecting isopropyl alcohol to the action of chlorine while maintaining a temperature between 35 C. and 70 C. and absorbing the vapor products of reaction in water.

5. In the process of forming chlorinated acetones, subjecting isopropyl alcohol to the action of chlorine in the presence of water whil] maintaining a temperature of above 35 6. In the rocess of forming chlorinated acetones, subjecting isopropyl alcohol to the action of chlorine while maintaining a temperature between 35 and 70 C., collecting the li uid products of reaction, separating the ch orinated acetones therefrom, absorbing the vapor products of reaction in water, separating the chlorinated acetones thereby absorbed, and combining the separated chlorinated acetones..

7. A mixture of chlorinated acetones derived from: the chlorination of iso ropyl alcohol and containing-10 ,to 20% o chlorinated hydrocarbons.

8. A mixture of chlorinated acetones comprising di and trichloracetones with some ico mesme I sym. tetrav and pentachloracetone, lsaid mixture having a specific gravity of 1.45 to 1.50 and containing not more than 20% of chlorinated hydrocarbons. l

9. ln thev process of forming' chlorinated acetones, subjecting isopropyl alcohol to the action of chlorine while maintaining a tem'- perature between 35 and 70 C., collecting the liquid products of reaction, separating 410 the chlorinated acetones therefrom, absorbing the vapor products of reaction in water, separating the chlorinated acetones thereby absorbed, combining the separated chlorinated acetones, and fraetionally distilling of? that portion of the chloracetone mixture boiling below 118 C., whereby the major portion of associated chlorinated hydrocarbons are removed.

IHHM E. Bric. 

